Structural analysis of a metallosupramolecular polyelectrolyte-amphiphile complex at the air/water interface

A detailed analysis of a metallosupramolecular coordination polyelectrolyte-amphiphile complex (PAC) at the air/water interface is presented based on Langmuir isotherm measurements, Brewster angle microscopy as well as X-ray reflectance and diffraction measurements. The PAC is prepared in solution by metal-ion coordination of Fe(OAc)2 and 1,4-bis(2,2':6',2"-terpyridin-4'-yl)benzene followed by self-assembly with dihexadecyl phosphate (DHP). The spreading of the PAC at the air/water interface results in a Langmuir film with a stratified architecture, such that DHP forms a monolayer on the water surface, while the metallosupramolecular coordination polyelectrolyte (MEPE) is immersed in the aqueous subphase. Electrostatic interactions of MEPE and DHP force the alkyl chains into an upright, hexagonal lattice even at low surface pressures. This work illustrates how supramolecular, colloidal, and surface chemistry can be combined to create complex architectures with tailored characteristics that may not be accessible through self-organization in the liquid phase.